CN104535695B - A kind of gas chromatography tandem mass spectrometry detects the method for phenol in cigarette mainstream flue gas, NNK and benzo [a] pyrene simultaneously - Google Patents
A kind of gas chromatography tandem mass spectrometry detects the method for phenol in cigarette mainstream flue gas, NNK and benzo [a] pyrene simultaneously Download PDFInfo
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Abstract
A kind of gas chromatography tandem mass spectrometry detects the method for phenol in cigarette mainstream flue gas, NNK and benzo [a] pyrene simultaneously, it is characterized in that: the method utilizes phenol, NNK and benzo [a] pyrene in cambridge filter trapping cigarette mainstream flue gas, with extraction solution, cambridge filter is extracted, adopt gas chromatography tandem mass spectrometry (GC-MS/MS) to detect extract, measure the content of phenol, NNK and benzo [a] pyrene in cigarette mainstream flue gas.Analysis determining method of the present invention is compared with the respective assay method of benzo [a] pyrene with phenol, NNK in existing cigarette mainstream flue gas, simplify sample pre-treatments, improve detection sensitivity, improve analytical test flux simultaneously, be applicable to the express-analysis of batch samples.
Description
Technical field
The invention belongs to cigarette smoke technical field of analysis and detection, be specifically related to a kind of method that gas chromatography tandem mass spectrometry detects phenol in cigarette mainstream flue gas, NNK and benzo [a] pyrene simultaneously.
Background technology
Along with " Framework Convention on Tobacco Control " signature and come into force, " control of tobacco product composition " and " regulation that tobacco product discloses " in pact impels signtory power to make the control regime of tobacco product security aspect, and more strictly limits the burst size of harmful ingredients in flue gas.In order to realize objective evaluation to cigarette smoke harmfulness and effective control, each research institution and researchist propose respective tobacco and harmful substances in flue gas list one after another.Tobacco monopoly bureau of China determines the 7 kinds of objectionable constituent lists characterizing cigarette harmfulness, i.e. CO, hydrogen cyanide, NNK, ammonia, benzo [a] pyrene, phenol, crotonaldehyde.
For the assay method of 7 kinds of objectionable constituent in cigarette smoke, all set up comparatively complete assay method standard at present, mainly comprise: the mensuration non-scatter infrared method of carbon monoxide " in the components in cigarette smoke gas phase ", the mensuration continuous flow method of hydrogen cyanide " in the cigarette mainstream flue gas ", " in cigarette mainstream smoke total particulate matter, the mensuration gas chromatography-heat energy of the peculiar N-nitrosamine of tobacco analyzes coupling method ", " the mensuration chromatography of ions of ammonia of main stream smoke of cigarette ", the mensuration of benzo [a] pyrene " in the cigarette smoke condensates ", " the mensuration high performance liquid chromatography of main phenolic compounds in main stream smoke of cigarette ", " the mensuration high performance liquid chromatography of main carbonyl compounds in main stream cigarette smoke " etc.Tobacco enterprise strictly will control the burst size of main objectionable constituent in cigarette smoke, and 7 kinds of objectionable constituent become the important content that each tobacco detects department's routine testing.But cigarette mainstream flue gas 7 kinds of objectionable constituent analytical approach systems contain 7 kinds of different analytical approachs, need instrument 6 to overlap, chemical reagent more than 30 is planted; These analytical approachs need operating personnel to have higher specialized capability, and through system training; Meanwhile, the cigarette sample amount of 7 kinds of objectionable constituent detections is large.Current, 7 kinds of objectionable constituent test jobs occupy a large amount of time and manpower, and the instrument and equipment quantity needed is many, and employ a large amount of solvents and reagent, testing cost is higher.Therefore, what the analytical approach developing multiple index in a kind of energy Simultaneously test 7 kinds of objectionable constituent just showed is necessary very much.Due to phenol, NNK and benzo [a] pyrene all can detect by gas chromatography-tandem mass spectrometry (GC-MS/MS), therefore, set up a kind of method adopting GC-MS/MS simultaneously to detect phenol in cigarette mainstream flue gas, NNK and benzo [a] pyrene, raising analysis efficiency is had great importance.
Summary of the invention
Object of the present invention detects for phenol, NNK and benzo [a] pyrene in cigarette mainstream flue gas just needs diverse ways, and the loaded down with trivial details time-consuming problem of sample pre-treatments, provide a kind of GC-MS/MS to detect the method for phenol in cigarette mainstream flue gas, NNK and benzo [a] pyrene simultaneously.
The object of the invention is to be realized by following scheme: a kind of gas chromatography tandem mass spectrometry detects phenol in cigarette mainstream flue gas simultaneously, the method of NNK and benzo [a] pyrene, utilize the phenol in cambridge filter trapping cigarette mainstream flue gas, NNK and benzo [a] pyrene, by phenol, NNK, the inner mark solution of benzo [a] pyrene and extractant join to collect to be had in the container of cambridge filter, cambridge filter is extracted, gas chromatography tandem mass spectrometry (GC-MS/MS) is adopted to detect extract, measure phenol in cigarette mainstream flue gas, the content of NNK and benzo [a] pyrene, concrete steps are as follows:
The trapping of phenol, NNK and benzo [a] pyrene and extraction in a, cigarette mainstream flue gas: the granule phase substance being trapped cigarette mainstream flue gas by cambridge filter, cambridge filter is placed in collection container, add phenol, NNK, the inner mark solution of benzo [a] pyrene and extractant, after ultrasonic or oscillation extraction, extract is passed through filter membrane, collect 0.5 ~ 2mL sample in chromatogram bottle, treat that GC-MS/MS detects;
The analysis of b, fume sample:
GC-MS/MS analysis condition: chromatography column feed materials mouth temperature: 260 DEG C; Sample size: 1 μ L; Input mode: Splitless injecting samples; Carrier gas: helium, constant current speed 1mL/min; Chromatographic column: DB-17MS (30m × 0.32mm × 0.25 μm); Temperature programme: initial temperature 50 DEG C, keeps 1min, rises to 80 DEG C with 2 DEG C/min; Rise to 230 DEG C with 20 DEG C/min, rise to 280 DEG C with 5 DEG C/min, keep 20min; Transmission line temperature: 280 DEG C; Mass spectrum ionization mode: EI; Ion source temperature: 250 DEG C; Scanning of the mass spectrum mode: multiple-reaction monitoring MRM pattern, collision gas: Ar gas, air pressure 1.5mTorr.
In cigarette mainstream flue gas phenol, NNK and benzo [a] pyrene trapping process in, cigarette adopts orthoscopic smoking machine or rotating disc type smoking machine respectively according to the suction of GB/T19609 and YC/T29-1996 specified standard condition, each experiment suction 20 cigarette.
In the present invention, the inner mark solution of described phenol, NNK, benzo [a] pyrene is the methanol solution of deuterated phenol, deuterated NNK, deuterated benzo [a] pyrene.
In the present invention, described collection container is the ground conical flask of 250mL; Described extractant is methyl alcohol, isopropyl alcohol, methylene chloride, cyclohexane or dilute hydrochloric acid solution, and the consumption of extractant is 20 ~ 100mL, and extraction mode is ultrasonic extraction or oscillation extraction, and extraction time is 10min ~ 1h.
In the present invention, described extract filtering membrane is aqueous phase or organic phase filter membrane, and filter sizes is 0.22 μm or 0.45 μm.
Utilize the inventive method Pyrogentisinic Acid, NNK, the reference material of benzo [a] pyrene and interior mark compound thereof to carry out mass spectrometry parameters optimization, relevant parameters is as shown in table 1 in the parent ion of compound, daughter ion and collision energy (CE) value:
Compared with prior art, the inventive method has following excellent results:
Because the present invention utilizes cambridge filter to trap the granule phase substance of cigarette mainstream flue gas, with extractant, cambridge filter is extracted again, extract directly adopts GC-MS/MS Quantitative Determination of Phenol, NNK and benzo [a] pyrene after membrane filtration, deuterated internal standard method is adopted to carry out quantitatively, make sample pre-treatments simple, and accuracy, reproducible.GC-MS/MS has the sensitivity of better selectivity and Geng Gao than GC-MS, is particularly suitable for the trace samplings analysis in complex matrices.The present invention can detect phenol in cigarette mainstream flue gas, NNK and benzo [a] pyrene simultaneously, and sample pre-treatments is simple, substantially increases the analysis throughput of sample.
Accompanying drawing explanation
The MRM figure of phenol, NNK and benzo [a] pyrene standard model quantitative and qualitative ion on GC-MS/MS in Fig. 1 the present invention.
In Fig. 2 the present invention, in cigarette sample main flume, the GC-MS/MS of phenol, NNK and benzo [a] pyrene detects MRM figure.
Embodiment
The present invention is described further below with reference to embodiment:
Balance and extract cigarette sample to be measured, adopting rotating disc type smoking machine according to the suction of YC/T29-1996 specified standard condition, trap the granule phase substance in 20 cigarette mainstream flue gas with cambridge filter.
Have the cambridge filter of granule phase substance to put into the ground conical flask of 250mL trapping, add 40mL methyl alcohol, add containing deuterated phenol (1mg/mL), deuterated NNK(1 μ g/mL), the methanol solution 200 μ L of deuterated benzo [a] pyrene (1 μ g/mL); By conical flask at room temperature ultrasonic extraction 30min, get the extract of 2mL, cross 0.22 μm of organic phase filter membrane, collect sample with chromatogram bottle, treat that GC-MS/MS analyzes.
GC-MS/MS analysis condition: chromatography column feed materials mouth temperature: 260 DEG C; Sample size: 1 μ L; Input mode: Splitless injecting samples; Carrier gas: helium, constant current speed 1mL/min; Chromatographic column: DB-17MS (30m × 0.32mm × 0.25 μm); Temperature programme: initial temperature 50 DEG C, keeps 1min, rises to 80 DEG C with 2 DEG C/min; Rise to 230 DEG C with 20 DEG C/min, rise to 280 DEG C with 5 DEG C/min, keep 20min; Transmission line temperature: 280 DEG C; Mass spectrum ionization mode: EI; Ion source temperature: 250 DEG C; Scanning of the mass spectrum mode: multiple-reaction monitoring MRM pattern, collision gas: Ar gas, air pressure 1.5mTorr.
Adopt the inventive method to measure the main flume of Virginian-type cigarette sample and blended type cigarette sample respectively, result is as shown in table 2:
Table 2GC-MS/MS is to the testing result of phenol, NNK and benzo [a] pyrene in cigarette sample main flume
By the GC-MS/MS testing result of phenol, NNK and benzo [a] pyrene compared with the testing result of its standard method separately, consistance is better, result error <10%.Result shows, GC-MS/MS method of the present invention detects phenol in cigarette mainstream flue gas, NNK and benzo [a] pyrene simultaneously and has higher accuracy; In addition, the method sample pre-treatments is simple, can detect the phenol of cigarette mainstream flue gas, NNK and benzo [a] pyrene simultaneously, substantially increase sample analysis flux.
Claims (5)
1. a gas chromatography tandem mass spectrometry detects phenol in cigarette mainstream flue gas simultaneously, the method of NNK and benzo [a] pyrene, it is characterized in that: the method utilizes the phenol in cambridge filter trapping cigarette mainstream flue gas, NNK and benzo [a] pyrene, by phenol, NNK, the inner mark solution of benzo [a] pyrene and extractant join to collect to be had in the container of cambridge filter, cambridge filter is extracted, gas chromatography tandem mass spectrometry (GC-MS/MS) is adopted to detect extract, measure phenol in cigarette mainstream flue gas, the content of NNK and benzo [a] pyrene, concrete steps are as follows:
The trapping of phenol, NNK and benzo [a] pyrene and extraction in a, cigarette mainstream flue gas: the granule phase substance being trapped cigarette mainstream flue gas by cambridge filter, cambridge filter is placed in collection container, add phenol, NNK, the inner mark solution of benzo [a] pyrene and extractant, after ultrasonic or oscillation extraction, extract is passed through filter membrane, collect 0.5 ~ 2mL sample in chromatogram bottle, treat that GC-MS/MS detects;
The analysis of b, fume sample:
GC-MS/MS analysis condition:
Chromatography column feed materials mouth temperature: 260 DEG C; Sample size: 1 μ L; Input mode: Splitless injecting samples; Carrier gas: helium, constant current speed 1mL/min; Chromatographic column: DB-17MS, specification 30m × 0.32mm × 0.25 μm; Temperature programme: initial temperature 50 DEG C, keeps 1min, rises to 80 DEG C with 2 DEG C/min; Rise to 230 DEG C with 20 DEG C/min, rise to 280 DEG C with 5 DEG C/min, keep 20min; Transmission line temperature: 280 DEG C;
Mass spectrum ionization mode: EI; Ion source temperature: 250 DEG C; Scanning of the mass spectrum mode: multiple-reaction monitoring MRM pattern; Collision gas: Ar gas, air pressure 1.5mTorr.
2. method according to claim 1, it is characterized in that: in the trapping process of cigarette mainstream flue gas phenol, NNK and benzo [a] pyrene, cigarette adopts orthoscopic smoking machine or rotating disc type smoking machine respectively according to the suction of GB/T19609 and YC/T29-1996 specified standard condition, each experiment suction 20 cigarette.
3. method according to claim 1, is characterized in that: in described method, the inner mark solution of phenol, NNK, benzo [a] pyrene is the methanol solution of deuterated phenol, deuterated NNK, deuterated benzo [a] pyrene.
4. method according to claim 1, it is characterized in that: the extractant of described method is methyl alcohol, isopropyl alcohol, methylene chloride, cyclohexane or dilute hydrochloric acid solution, the consumption of extractant is 20 ~ 100mL, and extraction mode is ultrasonic extraction or oscillation extraction, and extraction time is 10min ~ 1h.
5. method according to claim 1, is characterized in that: the filtering membrane of described extract is aqueous phase or organic phase filter membrane, and filter sizes is 0.22 μm or 0.45 μm.
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| CN107907617A (en) * | 2017-06-15 | 2018-04-13 | 中国烟草总公司贵州省公司 | It is a kind of to trap the method for phenolic compound and ammonia in cigarette mainstream flue gas at the same time using liquid feeding filter disc is in situ |
| CN109975467B (en) * | 2017-12-28 | 2023-05-02 | 贵州中烟工业有限责任公司 | Method for measuring epoxypropanol in main stream smoke of cigarette |
| CN108445112B (en) * | 2018-05-29 | 2021-03-16 | 云南中烟工业有限责任公司 | Method for detecting 4- (N-methyl-N-nitrosamine) -1- (3-pyridyl) -butanone in tobacco smoke |
| CN113109472B (en) * | 2021-04-13 | 2023-03-14 | 中国烟草总公司郑州烟草研究院 | Novel method for simultaneously measuring main chemical components and phenolic harmful components in smoke exhaled by tobacco products |
| CN113567533A (en) * | 2021-07-22 | 2021-10-29 | 上海市口腔医院(上海市口腔健康中心) | Quantitative detection method of plant histone variant H3.3 based on MRM |
| CN115728398A (en) * | 2021-08-26 | 2023-03-03 | 贵州中烟工业有限责任公司 | Method for measuring nicotine and volatile phenol in smoke intercepted by cigarette filter |
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